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Theoretical Study on the Stable Structures and Aromaticities for Pnictogen Dianionic Sb42-, Bi42-, and (SbBi)22- Clusters
Xing-bao Wang,Xian-xing Chi *
Author NameAffiliationE-mail
Xing-bao Wang School of Physics and Electronic Information, Wenzhou University, Wenzhou 325027, China  
Xian-xing Chi * School of Physics and Electronic Information, Wenzhou University, Wenzhou 325027, China chixx@wzu.edu.cn 
Abstract:
Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory (B3LYP) and two post- Hartree-Fock approaches (MP2, CCSD(T)), several stable isomers for new three pnictogendianionic Sb42-, Bi42-, and (SbBi)22- species were determined. For two homoatomic Sb42- and Bi42- species, there are three stable isomers: square (D4h), roof-shaped (C2v-1), and C2v-2 structure with the square isomer being the ground state. For the heteroatomic dian- ionic (SbBi)22- species, there are also three stable isomers: rhombus (D2h), roof-shaped (C1), and C2v structures with the rhombic isomer being the ground state. The calculated NICS values show that nucleus-independent chemical shifts (NICS) values of roof-shaped isomers for Sb42-, Bi42-, and (SbBi)22- species are all negative, consequently indicating that these roof-shaped isomers possess aromaticities. NICS values for the planar ring isomers are all positive, suggesting that these three planar ring isomers have antiaromatic characters. The aromaticity for the two stable roof-shaped and square isomers are preliminarily explained and discussed with MO analysis.
Key words:  Pnictogen cluster, Ab initio, Aromaticity, Nucleus-independent chemical shift
FundProject:
Theoretical Study on the Stable Structures and Aromaticities for Pnictogen Dianionic Sb42-, Bi42-, and (SbBi)22- Clusters
王兴保,池贤兴 *
摘要:
运用密度泛函方法(B3LYP)和后Hartree-Fock (post-HF:MP2、CCSD(T)),对三个新的磷属二价阴离子团簇Sb42-、Bi42-和(SbBi)22-的几个可能的同分异构体进行结构优化、振动频率和原子化能的理论计算.计算结果表明Sb42-和Bi42-团簇有三种稳定的结构:正方形(D4h)、屋顶型(roof,C2v-1)和C2v-2结构,其中正方形结构是基态.由异原子组成的(SbBi)22-团簇也有三种稳定结构:菱形(D4h)、屋顶型(roof,C1)和C2v结构,其中菱形结构是基态.计算显示Sb42-、Bi42-和(SbBi)22-团簇的所有屋顶型(roof)结构的核独立化学位移(NICS)全部为负值,从而说明这些屋顶型结构拥有芳香性;平面环结构(正方形或菱形)的核独立化学位移值全部为正值,说明这三种平面环结构具有反芳香性.用分子轨道分析对这两类屋顶型和平面环结构的芳香性和反芳香性作了解释和讨论.
关键词:  磷属团簇,从头算,芳香性,核独立化学位移
DOI:10.1088/1674-0068/22/01/75-81
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